TW201009164A - Composition and process for whitening paper - Google Patents

Abstract

The invention relates to a composition suitable for surface treatment of paper, wherein the composition contains a specified fluorescent whitening agent with alkylsulfonic acid groups, a salt of a bivalent cation, and a carrier. The composition is used for whitening paper, in particular in the size press.

Description

201009164 VI. Description of the invention: Technology of the invention belongs to the invention 3 The invention relates to a composition suitable for the surface treatment of paper, in particular, a size press liqU〇r, and a composition for using the composition The method of whitening paper.

匚Prior Art J In the manufacture of paper, the sizing step is usually used to achieve good writing and printing properties and strength. On the one hand, this sizing step can be carried out in the pulp before the sheet forming (internal sizing); on the other hand, it can be carried out in the size press after the sheet is formed. . A combination of the two methods is also possible. In one or two stages of manufacture of the paper, whitening of the pulp or paper is usually also carried out using a fluorescent whitening agent (FWA). Typically, in the case of pulp application, the slurry and fluorescent whitening agent are applied separately to the pulp; in the case of surface damage, the fluorescent whitening agent is blended into the sizing press and applied together with the upper press. To paper. The combination of surface sizing and whitening of paper is widely used in the paper industry. This method is particularly widely used in printing paper and writing paper (photocopying 'inkjet printing, lithographic printing, etc.). The continuous trend of surface sizing paper is expected to have high whiteness and improved printing efficiency. As a result, sizing press liquid is required to be as effective as possible. . US 6,207,258 B1 discloses a composition and method for improving ink jet printing performance using a divalent metal salt, particularly calcium carbonate. Therefore, in order to achieve brighter and more vivid printing, especially for inkjet printing, the paper industry today uses gasified calcium in sizing presses. However, the use of such a salt adversely affects the efficacy of the fluorescent whitening agent commonly used in sizing presses. In particular, the whitening effect is reduced, and the hue is biased toward the green 3 201009164 yellow direction, and the additional loss of fluorescence is observed. Unexpectedly 'discovering a specific hydrazine containing alkyl sulfonic acid group _ triphosphoryl amine _ stilbene compound when combined with a divalent cation salt such as calcium chloride for a composition suitable for surface treatment of paper such as sizing press Liquid can overcome the problems of the prior art. SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a composition suitable for surface treatment of paper, wherein the composition contains (a) at least one fluorescent whitening agent of formula (I)

m and η represent an integer from 0 to 3, respectively; R!, R2, R3, R4, R5 and R6 represent hydrogen, cyano, Ci_Q^, C1-C4, and CVC4, respectively. (^2_(^4 is calcined, wherein the base is linear or unbranched, or R3 and R4 or with a nitrogen atom respectively form a porphyrin ring, a piperidine ring or a "pyrrolidine ring"; or, where i is 1 , 2 or 3; or

Wherein -S〇3M group may be an integer from 丨 to 3 in the ortho, meta or para position, or -(Ci-Cj stretching base)-COOR, -(CVQ extension base)_c〇NHR, 201009164 - (Ci-C* Stretching base)-C〇R, preferably -(CH2)i-COOR, -(CH2)i-' comm' _(cH2)rc〇R, wherein the alkyl group is linear or branched, i is an integer from i to 4, RacVCs alkyl or equal to μ; Μ represents hydrogen, or one equivalent of a cation, particularly Li, Na, κ, Ca, Mg, ammonium, or an arcc4 or a C2-C4 hydroxyalkyl group One-, two-, three- or four-substituted money; (b) at least one divalent cation salt; φ (c) at least one carrier; and (d) water. SUMMARY OF THE INVENTION The present invention is directed to a method for whitening paper wherein the cellulose sheet is in contact with a composition as defined above, preferably in contact with a sizing press. The preferred embodiments of the present invention are described in the following embodiments, claims, and drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the effect of vaporized calcium on the efficacy of different fluorescent whitening agents according to Example 1. Figure 2 is a schematic diagram showing the effect of different divalent cation salts on the efficacy of different fluorescent whitening agents according to Example 2. Figure 3 is a still further image showing the effect of vaporized calcium on the performance of the different fluorescent whitening agents according to Example 3. In the preferred embodiment of the present invention, the composition suitable for the surface treatment of paper is a superior press liquid, and the method is a method for whitening paper in an upper poly-press machine. Wherein the cellulose sheet is in contact with the upper pressure booth 5 201009164 liquid 0. In the context of the present invention, it is understood that the sizing press means that the surface application unit is preferably a surface application unit of the paper machine. The sheet paper is contacted with the sizing press liquid, and the proportion of the liquid (liquid absorption) absorbed by the sheet of paper is preferably adjusted by the roll pressure. Recently, the development of sizing presses or film presses, namely the speed sizing machine (Symsizer) and the symmetrical sizing machine (Symsizer) and the brake roll (Gate_r〇u), must also be understood to cover the sizing press. The scope of the word. The composition according to the present invention contains at least one of the cold-di-sigma-indenyl-monostyrene compounds of the formula (1) as defined above, wherein 11, 111, 111 to 1^6, and the river system are as defined above. In a preferred embodiment, η and m are integers from 1 to 2, and most preferably 1. In another preferred embodiment, R丨, r2, r3, r4, heart and heart represent hydrogen 'CVC4 alkyl, CVC4 hydroxyalkyl, respectively, wherein alkyl is linear or branched, -(CHJ-SC^M, 1 is 1, 2 or 3, or 'X] [^-(S〇3M)k ϊ where the -S〇3M base can be in the ortho, meta or para position and let it be an integer from 3 to 3, more Preferably, η and m are in another preferred embodiment, the heart and the heart are -CH2CH2S03M', wherein the preferred group is! In another preferred embodiment, Rl, R2, R4 and R6 are hydrogen and Both the ruler 3 and the ruler 5 are CH2CH2S〇3M, wherein preferably η and m are 1. In another preferred embodiment, Ri, R2, heart and r6 are hydrogen and rar5 are both _s〇3M& Substituting a phenyl group at the 2,5_ position, wherein preferably η and m are 1. In another preferred embodiment, at least one of &, R2, R4 or the heart is _(CH2)rS〇 3M, i is Bu 2 or 3, and 201009164 R3 and R5 are both -ch2ch2so3m. Preferred embodiments of M are hydrogen, Na, K, Ca, Mg, wherein MgNa or K' is preferably Na. Formula (1) Fluorescence Brighteners can be made according to known procedures. For example, gb 1,010,759 describes the preparation of such compounds. Typically these compounds are via cyanuric chloride and 4,4,-diamine stilbene 2,2,di-disulfonic acid or a salt thereof, and a suitable sulfonic acid derivative such as an alkane-sulfonic acid or a salt thereof The composition of the present invention may contain more than one, preferably two or three, and most preferably three kinds of fluorescent whitening agents of the formula (I). In addition to at least one fluorescent whitening agent of the formula (I), the composition Component (a) contains one or more known fluorene-tri-glycolamine-stilbene or a fluorinated brightener based on distyryl-phenyl. The components of the composition of the present invention. (b) The salt comprises a divalent cation, preferably an alkaline earth metal cation, especially calcium or magnesium. Preferably, the counter ion of the divalent cation is a monovalent or polyvalent anion, particularly a halide anion, a sulfate, a hydrogen sulfate, Phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, Weigen, (tetra) or mixtures thereof, preferred anion or thioglycan, and most preferably chloride anion. disclosed in US 6,207,258 B1 Salt is also suitable. The preferred salt is gasification 33, gas (10), sulfur secret, or a mixture thereof, more preferably gas, gas, gas Magnesium, or a mixture thereof; and preferably a chlorinated dance. The carrier of _, 'and the knife (c) is known to be suitable for use as a carrier in the art, and is particularly suitable for use as a carrier for the squeezing press. A compound. The preferred carrier is slow methyl cellulose (CMC), polyethoxyethanol (pvA), powder or a mixture thereof, 201009164; the powder is particularly good. The suitable carrier material is, for example, a hydrogen bridge. a hydrophilic polymer of a bond. Preferred carrier materials are starch, polyvinyl alcohol, carboxymethyl cellulose, and polyethylene glycol having a number average molecular weight of from 2 Å to 8,000 g/mol. Any desired mixture of such materials, which may also be modified as desired. Preferably, the polyvinyl alcohol has a degree of hydrolysis of greater than 85%. Preferably, the carboxymethylcellulose has a degree of substitution DS of greater than 0.5. Polyethylene glycol having a number average molecular weight Μη of from 200 to 8000 g/mol is preferred. Suitable starches, for example, but not exclusively, are potato starch, rice starch, wheat starch, corn starch or tapioca starch. In particular, starch having a molecular weight that has been partially decomposed and/or derived by derivatization is preferably used in place of native starch. In addition, the two modification steps have been combined, i.e., starch which has been partially decomposed and additionally derivatized is suitable. Typical methods for the decomposition of starch are, for example, enzyme treatment, oxidation treatment, heat treatment or hydrolysis treatment. An example of a suitable starch derivative is hydroxyethyl starch or cationic starch. The composition of the present invention contains (d) water as a component thereof, and may optionally contain a sizing agent such as an alkenyl ketene binary alkyl ketene binary (AKD) or an alkenyl succinic anhydride (ASA). Rosin paste, styrene maleic anhydride copolymer, styrene acrylate, styrene acrylic copolymer, polyurethane or ethylene acrylic acid copolymer or other common paper chemicals such as styryl-acrylate copolymer , a latex, a pigment, an antifoaming agent, or a salt such as sodium chloride or sodium hydrogencarbonate, or a mixture of two or more thereof. The composition of the present invention preferably contains the component (8) in an amount of from 0.02 to 3, more preferably from 0.05 to 2, and most preferably from 〇1 to 1 wt%, based on 100% by weight (wt-%) of the composition. If a fluorescent whitening agent other than the compound of the formula (I) is used, 201009164 is used in an amount of from 5 to 95% by weight based on 100% by weight of the component (8). The component (b) is preferably present in an amount of from 02 to 8, particularly from 〇 5 to 6, and most preferably from 1 to 5 wt-%, based on the i 〇〇 wt % composition. The component is preferably present in an amount of from 3 to 20, particularly from 5 to 15, and most preferably from 6 to 12% by weight based on the i〇〇wt-% composition. The composition of the present invention preferably contains water at a level of from 96.78 Å, particularly from 79 to 94.45, and most preferably from 82.5 to 92.9 wt-%, based on 100 wt% of the composition. Optionally, the composition may contain a slurry of φ from 〇 to 5, particularly from 0 to 4, and preferably from 〇 to 3 wt%, based on the composition of 1 〇〇 wt _ %. In addition, relatively small amounts of additional adjuvants such as dispersants, extenders, anti-agents, preservatives, complexing agents, etc., which are generally present in amounts less than 5% by weight, or from the fluorescent whitening agent synthesis process are not subsequently processed The organic by-products which are completely removed may be included in the composition of the present invention. Suitable compositions are also described in us 6,207,258 B1, wherein at least one of the fluorescent whitening agents of formula (1) is used as a component (&) according to the present invention. The manufacture of the composition can be carried out by known methods, preferably by combining an aqueous solution of a fluorescent whitening agent comprising φ as component (a), preferably having an appropriate pH, with other components, such as carrier materials, Performed with sizing agents, binders, pigments, salts or standard chemicals. Preferably, an aqueous preparation of the carrier component (c) is prepared, and an aqueous preparation of the component (b) is added to the preparation, followed by the addition of the aqueous preparation of the fluorescent whitening agent component (a). Adjust to appropriate values and add other components. The method for whitening paper of the present invention is preferably carried out using a sizing press according to known methods, but is not limited. The paper to be used is not particularly limited and may be any type of cellulose sheet. 9 201009164 Paper obtained by the method of the present invention has improved whiteness in addition to improved printing performance and is therefore particularly suitable for use in ink jet printing applications. The whiteness of the paper produced can be characterized by CIE whiteness. When measured according to CIE whiteness, different fluorescent whitening agents can be compared to each other for saturation performance. In other words, if a larger amount of fluorescent whitening agent is used, and no further increase in whiteness is found, it is a saturated expression, and even a higher amount is used to adversely affect whiteness. The saturation effect is also referred to as greening. The greening limit, that is, the increase in the amount of fluorescent whitening agent does not substantially cause the whiteness to increase further, can be derived from the a*-b* map, where a* and b* are CIE-L*a*-b* color The color coordinates in the coordinate system. The following examples are illustrative of the invention and are intended to illustrate and not to limit the scope of the invention. EXAMPLES Example 1 The whitening performance of different fluorescent whitening agents in the presence of calcium chloride was investigated using the test procedure applied to the sizing press described below. First, a 15% starch solution (Perfec-tamyl 4692) and a 50% calcium carbonate solution of a neutral oxidatively decomposed potato starch were prepared. The paper used is 80 g/m2 of base paper, which is machine-made paper, which is internally aggregated (Ceber (c〇(10) equals 110 g/square illusion and slightly light fluorescent whitening (4)" has the following optical characteristics: CIE- 1〇4.89 ; L* = 93.92 ; a*=1 21 ; b*= 4 %. Weigh the fluorescent brightener in a glass, add 13 33 g of 15% powder solution, then weigh 50% Reducing the solution, adding water to the solution to 2 g. Therefore, the test is carried out in the service powder solution. After a short time of mixing, the solution is applied to the 10 201009164 semi-automatic laboratory coating machine with Rakel (No. 2). On one side of the base paper, the coater simulates the application of a film press. 1.7 g/m2 of dry starch is applied to the base paper. After stretching, the paper is directly dried on a drying drum at about 10 ° C. After the weather has been adapted overnight, the prepared side of the paper is measured by CIE, L*, a* and b* using a Datacolor spectrometer (IS02469), and the light source used is in accordance with the IS02469 standard. Relative to every 100 g of starch. The dosage of the preparation, the fluorescent whitening agent was 0.28 g and 0.56 g, respectively; the amount of calcium carbonate was 0 g and 2 g, respectively. Firefly optical brighteners by the following:

11 201009164

The results obtained are summarized in Table 1.

Table 1

Content in FWA starch preparation (wt %) CIE Whiteness L* a* b* ACIE CaCl2 FWA FWA 1 0 0.28 126.13 93.66 2.42 -9.15 1.93 2 0.28 128.06 93.72 2.42 -9.56 0 0.56 132.94 93.84 2.66 -10.59 0.11 2 0.56 133.05 94.03 2.37 -10.53 FWA 2 0 0.28 125.49 93.66 2.44 -9.01 1.02 2 0.28 126.51 93.67 2.42 -9.23 0 0.56 132.94 93.88 2.77 -10.58 -0.10 2 0.56 132.84 93.95 2.59 -10.52 Comparative example 1 0 0.28 124.88 93.86 1.84 -8.78 -4.52 2 0.28 120.36 93.95 0.94 -7.74 0 0.56 127.34 94.18 1.31 -9.18 -7.68 2 0.56 119.66 94.29 -0.09 -7.42 Comparative Example 2 0 0.28 127.95 93.74 2.30 -9.52 -0.85 2 0.28 127.10 93.86 1.93 -9.27 0 0.56 134.57 93.98 2.41 -10.89 - 3.89 2 0.56 130.68 94.16 1.61 -9.93 Comparative Example 3 0 0.28 127.00 93.77 2.05 -9.30 -1.50 12 201009164 2 0.28 125.50 94.00 1.37 -8.86 0 0.56 134.21 94.13 2.06 -10.74 -8.61 2 0.56 125.60 94.37 0.33 -8.70

As can be seen from Table 1, all of the fluorescent brighteners used in the FWA 1 and FWA 2 containing the bovine bilirubin (bovine acid, amine ethanoic acid) group, that is, the alkyl sulfonate group, are used. The concentration is shown in the coexistence of vaporized calcium, and the whiteness is improved (ACIE is positive). This is known, for example, by comparing the values of 0.28 wt-% FWA with and without chlorination. On the other hand, Comparative Examples FWA 1 to 3 showed a significant decrease in whiteness (ACIE was a negative value). For further illustration, the results of Table 1 are also shown in the outline of Figure 1. The foregoing data show that the use of a base having a sulphur-based acid group, particularly a bovine-bilirubin group, a tri-nurgical amine-stilbene fluorescent whitening agent, can be obtained with improved whiteness in the presence of a divalent cation salt, particularly calcium carbonate. Paper. Example 2 The whitening performance of the FWA of the present invention and the comparative example FWA has been studied in the presence of divalent cation calcium, magnesium and barium salts (CaCl2, MgCl2 and BaCl2). The test procedure is the same test procedure used in Example 1. As shown in Table 2 below, the amount of the salt was 0 g and 2 g based on 100 g of the starch preparation. The amount of FWA used was 0.28 g based on 1 g of the starch preparation. The FWA of the present invention is FWA3 having the following formula:

13 201009164 FWA3 For comparison, use Comparative Example 1 as described in Example 1 as fwa. The results obtained are shown in Table 2 below and further shown in Figure 2. Table 2 Salt content in FWA salt starch preparation (wt%) CIE Whiteness L* a* b* Δ CIE FWA3 0 ----- 122.2 94.0 2.06 -8.61 FWA3 CaCl2 2 123.70 94.07 1.69 -8.43 1.5 MgCl2 2 124.77 94.00 1.88 -8.70 2.57 BaCl2 2 124.12 94.03 1.79 -8.54 1.92 Comparative Example 1 - 0 122.94 94.13 1.62 -8.23 Comparative Example 1 CaCl2 2 118.07 94.18 0.70 -7.12 -4.87 MgCl2 2 119.76 94.16 1.05 -7.51 -3.18 BaCl2 2 119.18 94.17 0.96 -7.38 -3.76 The foregoing experimental results confirmed the use of calcium chloride and other divalent cation salts to obtain an improved whitening effect in the presence of a divalent cation salt. Example 3 The whitening efficacy of the different FWAs of the present invention and the comparative example FWA in the presence of vaporized calcium was investigated. The test program is the same test program used by the instance. Based on the 100g powder formula, the amount of gasification mother is 2 grams and 2 grams, as indicated in Table 3 below. The FWA dosage was 0.28 grams based on 100 grams of starch formulation, as indicated in Table 3 below. The FWA of the present invention is FWA1 and FWA as described in Example 1, FWA3 as described in Example 2, and further FWA4 as follows: 14 201009164

FWA 4 was used for comparison, and Comparative Example 1 and Comparative Example 2 as described in Example 1 were used as FWA. The results obtained are illustrated in Table 3 below and further shown in Figure 3. Table 3 Content in FWA Starch Formulation (wt %) CIE Whiteness L* a* b* Δ CIE CaCl2 FWA FWA1 0 0.28 124.88 93.74 2.39 -8.84 2.25 2 0.28 127.13 93.85 2.39 -9.29 FWA2 0 0.28 124.13 93.66 2.43 -8.71 2.64 2 0.28 126.77 93.79 2.45 -9.24 FWA3 0 0.28 126.27 93.72 2.35 -9.16 0.92 2 0.28 127.19 93.97 1.98 -9.25 FWA4 0 0.28 128.58 93.80 2.50 -9.64 0.90 2 0.28 129.48 93.89 2.43 -9.80 Comparative example 1 0 0.28 124.88 93.86 1.84 -8.78 - 4.52 2 0.28 120.36 93.95 0.94 -7.74 Comparative Example 2 0 0.28 128.02 93.82 2.31 -9.50 -0.72 2 0.28 127.30 93.96 1.91 -9.28

t: Simple description of the figure 3 Fig. 1 is a schematic view showing the effect of vaporized calcium on the performance of different fluorescent whitening agents according to Example 1. Figure 2 is a schematic diagram showing the effect of different divalent cation salts on the efficacy of the brighteners according to Example 2, 201009164. Figure 3 is a still further image showing the effect of vaporized calcium on the performance of the different fluorescent whitening agents according to Example 3. [Main component symbol description] (none)

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Claims (1)

201009164 VII. Patent application scope: 1. A composition suitable for surface treatment of paper, wherein the composition contains (a) at least one fluorescent whitening agent of formula (I) R2 SO, Μ where m and η represent an integer from 0 to 3, respectively; R1, R2, R~3, R4, R5 and R6 each represent a nitrogen, a chloro group, a C1-C4 alkyl group, a CVC4 alkoxy group, a Q-C4 hydroxyalkyl group, preferably a c2-c4 hydroxyalkyl group, wherein the alkane The base is linear or branched; or R3 and R4 or R5 and R6, respectively, together with the nitrogen atom form a taste ring, a ° 11 ring or a ratio σ of 11 rings; or -(CH2)rS03M, where 1 is 1, 2 Or 3; or x> -(SOgM)k wherein -S03M may be in the ortho, meta or para position and k is an integer from 1 to 3; or -(CVC4alkyl)-COOR, -(CVQ Alkyl)-CONHR, -(QQ alkylene)-COR, preferably -(CHA-COOR, -(CH2)rCONHR, -(CH2)i-COR, wherein alkylene is linear or branched, i is An integer from 1 to 4, 11 is (: 1-(: 3 alkyl or equal to Μ; 17 201009164 Μ represents hydrogen, or one equivalent of cation, especially Li, Na, cesium, Ca, Mg, ammonium, or by CrC4 a mono-, di-, tri- or tetra-substituted ammonium alkyl or C2-C4 hydroxyalkyl group; (b) at least one divalent cation salt; (c) at least one carrier; and (d) water. For example, the composition of the first paragraph of the patent application, wherein η and m are 1, and R3 and r5 are both -ch2ch2so3m. The composition of the second item, wherein &, R2, R4 and R6 are hydrogen. 4. The composition of claim 1 wherein η and R2, R4 and R6 are hydrogen, and R3 and R5 are Substituting two -so3m groups for the stylistic base at the 2,5-position. 5. The composition of claim 1 or 2, wherein R3 and R5 are both -CH2CH2S03M, and R!, R2, R4 or At least one of R6 is -(CH2)k-S03M, and k is 1, 2 or 3. 6. A composition according to any one of the preceding claims, wherein Μ is Na or Κ. The composition of any one of the preceding claims, wherein the salt of component (b) is calcium chloride. 8. The composition of any of the preceding claims, wherein component (c) The carrier is selected from the group consisting of carboxymethyl cellulose, polyvinyl alcohol, starch, and mixtures thereof. 9. The composition of claim 8, wherein the carrier is starch. 201009164 - ιο· A composition according to any one of the preceding claims, wherein the group of ingredients comprises component (a) in an amount of from 0.02 to 3% by weight, component (b) in an amount of from 0.2 to 8% by weight, and from 3 to 2 The component (c) in an amount of 0% by weight, each based on 100% by weight of the composition. The composition according to any one of the preceding claims, wherein the composition is an upper paddle press ( Size press liquor). 12. The composition of claim 11, wherein the composition comprises a sizing agent, a method for whitening paper, wherein the sheet of cellulose is in contact with A composition as defined in any one of the preceding claims. 14. The method of claim 13, wherein the contacting is performed on a size press. • 15. — A type of paper obtained by the method of claim 13 or 14 of the patent application. 19